Comminuted inorganic materials

ABSTRACT

According to the present invention a composition of matter is provided comprising the reaction product of a comminuted inorganic material and a substituted succinic anhydride having the formula: ##STR1## wherein at least one of R 1 , R 2 , R 3  and R 4  is a substituent selected from alkyl, alkenyl, alkynyl or aralkyl group having from 1 to about 30 carbon atoms or a substituted derivative thereof, and the remaining substituents are hydrogens. The substituent may be saturated or unsaturated, linear or branched, and may have from 1 to about 10 substitutions including halogen, tertiary amino, tertiary amide, ketal, episulfide, sulfonate, phosphonate, imide, carboxylate, carbonate, isocyanate, silane, epoxy, cyano, ether, thioether, carbonyl, aromatic nitro, or acetal. In a particular molecule, all of the R 1 , R 2 , R 3  and R 4  groups may be the same or different, so long as they fall within the above class.

The present invention relates to comminuted inorganic materials whichhave been treated with a substituted succinic anhydride. The presentinvention also relates to filled polymeric compositions wherein thefiller has been treated with a substituted succinic anhydride prior toincorporation into the polymer.

Inorganic materials have long been used as fillers, pigments,reinforcements and chemical reactants in polymers. In general, theseinorganic materials are hydrophilic, that is, easily wetted by water orable to absorb water, but their compatibility with organic polymers islimited. Because of this limited compatibility, the full potential ofcolor, reinforcement, or chemical reactivity of the inorganic materialsis not realized.

To overcome these difficulties, wetting agents have been used tominimize interfacial tension; but wetting agents, too, have seriousdeficiencies. In particular, relatively large proportions are necessaryto produce adequate wetting of the finely divided inorganics. When usedin large proportions, the wetting agents markedly detract from theproperties of the finished composite.

Coupling agents have been developed to overcome this difficulty.Coupling agents are used as a surface treatment for fillers to enhancethe interaction of the polymers with the fillers, and thus improve thephysical properties of the product. The coupling agent may bephysisorbed, chemisorbed, ionically bound or covalently bound to thefiller surface. The interaction with the polymer may be covalent, polar,van der Waals, or chain entanglement. Typical effects of coupling agentsare reduced viscosity of the filled polymer system, better dispersion ofthe fillers, higher impact, flexural and tensile strength, and bettersurface appearance of the filled product. They frequently make possiblehigher filler loadings without the associated processing troubles andproperty losses.

Known coupling agents fall into two general classes. The first, the morewidely used, is trialkoxy organo functional silanes. Their activity isbased upon chemical interaction between the alkoxy portion of the silaneand filler and the chemical reaction of the organo functional portionwith the polymer matrix. This provides a direct chemical link betweenthe polymer and filler. Their principal area of use has been in glassfiller reinforcement applications, particularly for polyester andrubber, and they perform relatively well in glass-filled systems.Silanes, however, have drawbacks. They are relatively expensive, andthey are typically highly flammable, difficult to handle, and not easilyworked into many polymer systems. Where the polymers do not containfunctional groups or where the filler does not contain acidic protons,the silanes are often ineffective because of their inability tointeract. For example, silanes are ineffective in the thermoplastichydrocarbons and with fillers such as carbon black, and to a largedegree calcium carbonate and sulfur.

The second group of coupling agents includes the organotitanates whichmay be prepared by reacting tetraalkyl titanates with aliphatic oraromatic carboxylic acids. Of particular interest are the di- ortrialkoxy acyl titanates or certain alkoxy triacyl titanates. Thesetitanates, however, have serious drawbacks. Frequently their effects maynot be uniform in different polymer systems so that experimentation maybe required among several titanates to discover the appropriate couplingagent for a given system. They also tend to decompose at temperaturesfrequently used in preparing many polymers; they tend to discolorcertain inorganic materials used with polymer systems; and they are notcompatible with many polymer systems.

Accordingly, the present invention provides new coupling agents whichare easily prepared from readily available starting materials and whichmay provide improved compatibility between inorganic filler materialsand organic polymers. Such improved compatibility may result in partfrom the ability of the anhydride moiety to scavange water from thesurface of the filler so that the resulting diacid binds tightly ontothe filler. Because of such improved compatibility, improved colorpotential, reinforcement and chemical reactivity of the inorganic fillermaterials may be realized. The new coupling agents of the presentinvention may not detract from the properties of the finished compositeand in fact they may actually serve to improve the physical propertiesof the product by, for instance, enhancing the interaction of thepolymers with the fillers. The coupling agents used in the preparationof the compositions of the present invention may be easily handled, andmay also be easily worked into many polymer systems. The coupling agentsused in the compositions of the present invention may be employed evenwhere the polymer system does not contain functional groups, e.g., inthermoplastic hydrocarbons or where the filler does not contain acidicprotons, e.g., carbon black, calcium carbonate and even sulfur. Thecoupling agents used in the compositions of the present invention arecompatible with a wide variety of polymer systems and may provide a moreuniform effect than many of the known titanate coupling agents. They arerelatively stable at the temperatures used to prepare the polymer; andthey generally do not discolor the inorganic materials used with thepolymer systems.

According to the present invention a composition of matter is providedcomprising the reaction product of a comminuted inorganic material and asubstituted succinic anhydride having the formula: ##STR2## wherein atleast one of R₁, R₂, R₃ and R₄ is a substituent selected from alkyl,alkenyl, alkynyl or aralkyl group having from 1 to about 30 carbon atomsor a substituted derivative thereof, and the remaining substituents arehydrogens. The substituent may be saturated or unsaturated, linear orbranched, and may have from 1 to about 10 substitutions includinghalogen, tertiary amino, tertiary amide, ketal, episulfide, sulfonate,phosphonate, imide, carboxylate, carbonate, isocyanate, silane, epoxy,cyano, ether, thioether, carbonyl, aromatic nitro, or acetal. In aparticular molecule, all of the R₁, R₂, R₃ and R₄ groups may be the sameor different, so long as they fall within the above class.

While a wide variety of substituents described herein may be employed,the most suitable may depend upon the filler/polymer system and to alesser extent upon the curative and/or extender systems employed. It ispreferred, however, that the substituent be alkenyl having 1 to about 22carbon atoms, e.g., hexenyl, octenyl, dodecenyl and octadecenyl. Suchcompounds are provided with an olefinic bond which may be capable ofreacting with the polymer into which the filler is incorporated.

Halo-substituted groups which may be employed include, for example,bromohexyl. One or more halogen atoms may be present, such as forexample difluorohexyl or tetrabromooctyl. Ester substituted aryl andalkyl groups include 4-carboxyethylcapryl and 3-carboxymethyl toluyl.

In addition to the foregoing aliphatic groups, groups containinghetero-atoms, such as oxygen, sulfur or nitrogen, in the chain may alsobe used. Examples of these radicals are ethers of the alkoxyalkyl type,including methoxyhexyl and ethoxydecyl. Alkylthioalkyl groups includemethylthiododecyl groups. Tertiary amines may also serve as the terminalportion of the hydrophobic group.

The aryl groups include the phenyl and naphthyl groups and substitutedderivatives. Substituted alkyl derivatives include toluyl, xylyl,pseudocumyl, mesityl, isodurenyl, durenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, cumyl, styryl, allylphenyl, nitro- andhalo-substituted may be exemplified by chloronitrophenyl,chlorodinitrophenyl, dinitrotoluol, and trinitroxylyl.

Substituted naphthyl groups include nitronaphthyl, chloronaphthyl andcarboxynaphthyl groups.

Halo-substituted aryl groups include fluoro-, chloro-, bromo-,iodophenyl, chlorotoluyl, bromotoluyl, methoxybromophenyl,dimethylaminobromophenyl, trichlorophenyl, bromochlorophenyl, andbromoiodophenyl.

Groups derived from aromatic carboxylic acids are also useful. Theseinclude methylcarboxylphenyl, dimethylaminocarboxyltoluyl,laurylcarboxyltoluyl and nitrocarboxyltoluyl.

Additional suitable groups include all oil epoxides (a mixture of fromabout 6 to about 22 carbon alkyl groups) containing an average of oneepoxy group per molecule and glycidyl ethers of lauryl or stearylalcohol.

Examples of the substituted succinic anhydrides of the inventioninclude: dodecenylsuccinic anhydride (DDSA), octadecenylsuccinicanhydride (ODSA) and1,4,5,6,7,7,-hexachloro-5-norbornene-2,3-dicarboxylic anhydride.

The substituted succinic anhydrides of the present invention may beeasily prepared by reacting maleic anhydride with a conjugated diene bywhat is known as a Diels-Alder reaction (see, for instance, equation 1below). ##STR3## Alternatively the anhydrides may be prepared by thereaction of maleic anhydride with α-methylene olefins, known as the"ene" reaction (see, for instance, equation 2 below). ##STR4##

The corresponding alkyl-substituted succinic anhydrides may be preparedby reacting the ethylenically unsaturated products produced by either ofthe above reactions with hydrogen to provide the correspondingalkyl-substituted compounds. The preferred coupling agents of thepresent invention, namely octadecenylsuccinic anhydride anddodecenylsuccinic anhydride may be conveniently prepared via reaction 2above from 1-octadecene and propylene tetramer (a mixture of isomers).

The composition of matter of the present invention comprises thereaction products of the aforesaid classes of substituted succinicanhydrides with inorganic materials. The amount of the substitutedsuccinic anhydride reacted may be at least 0.01 part, preferably from0.1 to 5 parts, and most preferably between 0.2 and 2 parts, per 100parts of inorganic solid. The optimum proportions required may be afunction of the inorganic solid and the substituted succinic anhydrideselected, and the degree of the comminution, i.e., the effective surfacearea, of the inorganic solid. The reaction of the substituted succinicanhydride may take place on the surface of the inorganic filler. Theanhydride moiety may scavange advantageous water from the fillersurface, and the resulting diacid may bind tightly to reactive sites onthe surface of the filler, or the anhydride may bind covalently withfree hydroxyl groups on the mineral surface forming a hydrophobicsurface layer on the inorganic solid. The unmodified inorganic solid maybe difficult to disperse in an organic medium because of its hydrophilicsurface. The substituted succinic anhydride compound may be incorporatedinto an organic medium (low molecular weight liquids or higher molecularweight polymeric solids) with the inorganic solid prior to reaction withthe inorganic solid if the substituted succinic anhydride and organicmedium are compatible. Alternatively, the substituted succinic anhydridemay be first reacted with the inorganic solid in the absence of anorganic medium and thereafter admixed with the latter.

By means of the present invention, the dispersion of inorganic materialsin organic polymer media, such as, for instance, nonprotic plastics, saypolyethylene, polypropylene and polyvinyl chloride is improved asevidenced by a substantially reduced viscosity of the filled polymersystem. Additional advantages which may be achieved include: (1)improved rheology or higher loading of the dispersate in the organicmedium; (2) higher degrees of reinforcement by the use of fillers,thereby resulting in improved physical properties in the filled polymer;(3) more efficient use of pigments and opacifiers; (4) higherinorganic-to-organic ratios in a dispersion; and (5) shorter mixingtimes to achieve dispersion.

Also, according to the invention herein, the reaction with a substitutedsuccinic anhydride may be carried out neat or in an organic medium toform a liquid, solid, or pastelike solid dispersion which can be used inthe compounding of the final polymeric system. Such dispersions are verystable, i.e., having little tendency to settle, separate, or harden onstorage to a non-dispersible state.

Moreover, the invention may simplify the making of inorganic dispersionsin organic media by providing a means to eliminate the solvent, toreduce the cost of processing equipment, and to reduce the time andenergy required to disperse an inorganic solid material in a liquid orpolymeric organic solid. The present invention may also result in theformation of a reinforced polymer which has a lower melt viscosity,improved physical properties, and better pigmenting characteristics thanthe prior art materials.

The practice of the present invention may achieve a product comprisingnatural or synthetic polymers which may contain particulate or fibrousinorganic materials which reinforce, pigment or chemically react withthe polymer to produce a product having superior physical properties,better processing characteristics and more efficient utilization ofpigments.

Among the advantages gained by the practice of this embodiment of thepresent invention is the option of dispensing with the use of volatileand flammable solvents and the attendant need to dry the filler or torecover solvents. Also, the dispersions of the present invention arenon-oxidizing.

The inorganic materials may be particulate or fibrous and of variedshape or size, so long as the surfaces are reactive with the substitutedsuccinic anhydride compound. Examples of inorganic reinforcing materialsinclude metals, clay, carbon black, calcium carbonate, barium sulfate,silica, mica, glass and asbestos. Reactive inorganic materials includethe metal oxides of zinc, magnesium, lead, and calcium and aluminum,iron filings and turnings, and sulfur. Examples of inorganic pigmentsinclude titanium dioxide, iron oxides, zinc chromate, ultramarine blue.As a practical matter, the particle size of the inorganic materialsshould not be greater than 1 mm, preferably from 0.1 micron to 500micron. The substituted succinic anhydride should be properly admixedwith the inorganic material to permit the surface of the latter to reactsufficiently. The optimum amount of the substituted succinic anhydrideto be used is dependent on the effect to be achieved, the availablesurface area of and the bonded water in the inorganic material.

Reaction is facilitated by admixing under the proper conditions. Optimumresults depend on the properties of the substituted succinic anhydride.The particle size, the geometry of the particles, the specific gravity,the chemical composition, among other things, must be considered.Additionally, the treated inorganic material must be thoroughly admixedwith the polymeric medium. The appropriate mixing conditions depend onthe type of polymer, whether it is thermoplastic or thermosetting, itschemical structure, etc., as will be readily understood by those skilledin the art.

Where the inorganic material is pretreated with the substituted succinicanhydride it may be admixed in any convenient type of intensive mixer,such as a Henschel or Hobart mixer or a Waring blender. Even hand mixingmay be employed. The optimum time and temperature are determined toobtain substantial reaction between the inorganic material and thesuccinic anhydride. Mixing may, for instance, be accomplished bydissolving the coupling agent in a solvent and adding the desired fillerto it. Then after stirring for a period of time sufficient for reactionto occur between the filler and the substituted succinic anhydride,e.g., at least about one hour, at a temperature which may be betweenabout room temperature and reflux, the solvent may be stripped and theproduct may then be dried at an elevated temperature, e.g., about 50° C.to 200° C., until it is dry, e.g., about 15 minutes to 5 hours. Severalother methods may also be suitable. For instance, the coupling agent maybe diluted with plasticizer or mineral oil and then coated onto thefiller in an agitated bed, e.g., high shear mixer. Application of thesubstituted succinic anhydride to certain fillers may be simplyaccomplished in water with heating and thorough drying of the product.In the latter instance the anhydride may hydrolyze to the diacid whichwould adhere to fillers with a basic surface. Additional methods may beapparent to those skilled in the art based upon the above disclosedtechniques. While it is desirable that the bulk of the reactive groupson the substituted succinic anhydride be reacted during the pretreatmentstep, this is not essential where the materials are later admixed with apolymer, since the substantial completion of the reaction may take placein this later mixing step.

Polymer processing, e.g., high shear mixing, is generally performed at atemperature well above the second order transition temperature of thepolymer, desirably at a temperature where the polymer will have a lowmelt viscosity. For example, low density polyethylene is best processedat a temperature range of 170° to 230° C.; high density polyethylenefrom 200° to 245° C.; polystyrene from 230° to 260° C.; andpolypropylene from 230° to 290° C. Temperatures for mixing otherpolymers are known to those skilled in the art and may be determined byreference to existing literature. A variety of mixing equipment may beused, e.g., two-roll mills, Banbury mixers, double concentric screws,counter or co-rotating twin screws and ZSK type of Werner and Pfaulderand Busse mixers.

When the substituted succinic anhydride and the inorganic materials aredry-blended, thorough mixing and/or reaction is not readily achieved andthe reaction may be substantially completed when the treated filler isadmixed with the polymer. In this latter step, the substituted succinicanhydride may also react with the polymeric material if one or more ofthe R₁, R₂, R₃ and R₄ groups is reactive with the polymer.

To illustrate further the invention, attention is directed to thefollowing examples where unless otherwise indicated parts andpercentages refer to parts and percentages by weight. It is to beunderstood that the examples are not to be construed as limiting theinvention, defined in the claims, in any way, but are for illustrativepurposes only.

EXAMPLE 1 Preparation of Dodecenylsuccinic Anhydride (DDSA)

Eleven hundred and ten grams (6.6 moles) of propylene tetramer and 430grams (4.4 moles) of maleic anhydride were placed in a 2 liter stirredautoclave equipped with a thermocouple. The reaction was carried out byheating the mixture at 255° C. for 3 hours, and the cooled product wastransferred to a 2 liter round bottom flask equipped with a magneticstir bar, a thermometer, and a distilling head mounted on a VigreuxColumn. Unreacted starting materials were removed at ˜200° C. and 10torr, followed by distillation of DDSA at 180°-240° C. (10 torr). Thefinal product (590 grams) was a pale yellow oil with a specific gravityof 1.00 g/ml and strong adsorption in its IR spectrum at 1860 and 1780cm⁻¹.

EXAMPLE 2 Preparation of Octadecenylsuccinic Anhydride (ODSA)

One thousand and eight grams (4.0 moles) of 1-octadecene and 490 grams(5.0 moles) of maleic anhydride were placed in a 2 liter stirredautoclave equipped with a thermocouple. The reaction was carried out byheating the mixture at 200° C. for 4 hours, and the cooled product wastransferred to a 2 liter round bottom flask equipped with a magneticstir bar, a thermometer, and a distilling head mounted on a VigreuxColumn. Unreacted starting materials were removed at 200° C. and 10torr, leaving the product ODSA (750 grams) in the pot. It was typicallya tan solid (m.p. 40°-55° C.) with strong adsorption in its IR spectrumat 1860 and 1785 cm⁻¹.

EXAMPLE 3

This example, summarized in Table 1 below, shows a comparison ofproperty modification using compounds of the present invention and thecompounds currently used commercially as coupling agents for CaCO₃ inlow density polyethylene. The compound of the invention used wasdodecenylsuccinic anhydride which was prepared as set forth in exampleabove. Four formulations were prepared using the same type ofpolyethylene and were compared to a sample of the unfilled polyethylene.Each of the four samples contained 60 parts by weight of low densitypolyethylene (NA 208, a trademark of U.S. Industrial Chemicals Co.), 40parts calcium carbonate filler having an average particle size of about2.5 microns (Microwhite 25, a trademark of Sylacauga Calcium Products),and one percent of the indicated coupling agent based on the weight ofthe filler. Each sample was extruded twice and injection molded. Incomposition 1, the calcium carbonate received no pretreatment. Incomposition 2, the calcium carbonate was pretreated with stearic acid.In composition 3, the calcium carbonate was pretreated with acommercially available titanate (KR-TTS, a trademark of KenrichPetrochemicals, Inc.). In composition 4, the calcium carbonate fillerwas pretreated with a substituted succinic anhydride of the invention.Results for the unfilled resin are also provided in Table 1.

                                      TABLE I                                     __________________________________________________________________________                       Composition No.                                                          Unfilled                                                                           1    2    3    4                                           __________________________________________________________________________    Tensile Strength (psi)                                                                      1530±40                                                                         1570±30                                                                         1450±10                                                                         1470±10                                                                         1420±10                                  Elongation at Break (%)                                                                     166±31                                                                          17±2                                                                            39±14                                                                           22±2                                                                            36±9                                     Impact Strength (ft.-lb./in.)                                                                    1.1±.3                                                                          2.7±.6                                                                          2.2±.2                                                                          2.5±.2                                   Flexural Modules (× 10.sup.4 psi)                                                     2.2±.5                                                                          5.8±.3                                                                          5.4±.3                                                                          5.3±.3                                                                          5.3±.3                                   __________________________________________________________________________

Within experimental error all of the coupling agents provided filledproducts that were comparable in tensile strength, percent elongation,impact strength and flexural modulus.

EXAMPLE 4

In this example, the results of which are summarized in Table II, theeffectiveness of a number of coupling agents and other dispersants todisperse 25 grams of coated calcium carbonate particles having anaverage particle size of about 2.5 microns (Microwhite 25, a trademarkof Sylacauga Calcium Products) in 50 grams of paraffin oil (viscosity of58 cps) by mixing at 20° C. with a Hamilton Beach mixer was determined.This test provides a means of determining the effectiveness of acoupling agent in improving the dispersion of inorganic materials in anorganic medium. In each instance one percent coupling agent wasemployed. In trails 12, 13, 16 and 18 coupling agents according to thepresent invention were employed. As Table II indicates, the mosteffective dispersants were dodecenylsuccinic anhydride (DDSA) andoctodecenylsuccinic anhydride (ODSA). The ability of an agent todisperse the inorganic particles in an organic medium may be a desirablefunction of a coupling agent especially where the inorganic particlesare not easily dispersed in the absence of such agents.

                  TABLE II                                                        ______________________________________                                        Trial                                                                              Dispersing or                                                            No.  Coupling Agent (1%)    Viscosity (cps)                                   ______________________________________                                        1.   None                   97,000                                            2.   Surfaid 79.sup.a       26,500                                            3.   CF.sub.3 CO.sub.2 H    8,750                                             4.   Dibenzo-18-crown-6     4,050                                             5.   C.sub.7 F.sub.15 CO.sub.2 H                                                                          2,600                                             6.   Dibenzo-18-crown-6 + 0.5% acetic acid                                                                2,050                                             7.   Tween 60               1,800                                             8.   Acetic acid (0.5%)     1,750                                             9.   VP 900.sup.b           1,725                                             10.  Chromium complex (Quilon C).sup.c                                                                    988                                               11.  VP 905.sup.b           625                                                     ##STR5##              575                                                     ##STR6##              525                                               14.  Stearic Acid           328                                               15.  Titanate (KR-TTS).sup.d                                                                              271                                               16.  ODSA                   259                                               17.  Lecithin               138                                               18.  DDSA                   100                                               ______________________________________                                         .sup.a NL Industries                                                          .sup.b Byk  Mallinckrodt Chemische                                            .sup.c E. I. DuPont de Nemours & Co.                                          .sup.d Kenrich Petrochemicals Inc.                                       

EXAMPLE 5

Example 4 was repeated using different fillers, i.e. Wollastonite,alumina trihydrate, and barium sulfate dispersed in paraffin oil andsimilar viscosity data was observed.

EXAMPLE 6

In this example the inorganic filler was precoated and dispersed in apolyol resin useful in making polyurethane foams. In each trial 50 gramsof Wollastonite (Nyad 400, a trademark of NYCO Co.) was precoated withthe coating indicated in column 2 of Table 3. The amount of coating isindicated in column 3 as percent based on the weight of filler. Theorganic medium was 50 grams of a polyol resin (Pluracol 381, a trademarkof Union Carbide Corp.) and the mixing was accomplished using a HamiltonBeach Blender. Viscosity data is provided both before and after theaddition of 1.1 milliliters of water (blowing agent) and againdodecenylsuccinic anhydride produced the lowest viscosity indicatingexcellent dispersion of the filler. As the example indicates, thisviscosity reduction may be especially important in reinforced reactioninjection molding (RRIM) applications.

                  TABLE III                                                       ______________________________________                                                                      Initial                                                                              Viscosity                                                     %        Viscosity                                                                            After H.sub.2 O                          Trial Coating        Loading  (cps)  Addition                                 ______________________________________                                        1.    None           --       3,250  40,750                                   2.    Stearic Acid   1.0      5,750  20,750                                   3.    Titanate (KR-TTS)**                                                                          0.5      4,000  4,750                                    4.    Lecithin       1.0      3,800  7,650                                    5.    Lecithin       0.5      2,000  4,450                                    6.    Silane (A-174)*                                                                              0.5      2,150  1,900                                    7.    Silane (A-1100)*                                                                             0.5      2,100  9,250                                    8.    Titanate (KR-55)**                                                                           0.5      2,100  4,250                                    9.    Polymeric ester***                                                                           0.5      1,650  8,250                                          (W-900)                                                                 10.   Titanate (KR-138)**                                                                          0.5      1,650  3,400                                    11.   DDSA           0.5      1,900  1,700                                    12.   DDSA           1.0      1,250  1,550                                    ______________________________________                                         *Union Carbide Corp.                                                          **Kenrich Petrochemicals Inc.                                                 ***BykMallinckrodt Chemische                                             

What is claimed is:
 1. A composition of matter which comprises acomminuted inorganic material which has been treated with a substitutedsuccinic anhydride of the formula: ##STR7## wherein at least one of R₁,R₂, R₃ and R₄ is a substituent selected from alkyl, alkenyl, alkynyl oraralkyl group having from 1 to about 30 carbon atoms or a substitutedderivative thereof, and the other substituents are hydrogens.
 2. Thecomposition of claim 1, wherein said substituent has from 1 to 10substitutions including halogen, tertiary amino, tertiary amide, ketal,episulfide, sulfonate, phosphonate, imide, carboxylate, carbonate,isocyanate, silane, epoxy, cyano, ether, thioether, carbonyl, aromaticnitro, and acetal.
 3. The composition of matter of claim 1, wherein saidcomminuted inorganic material is a filler which is a metal, metal oxide,carbon black, sulfur, calcium carbonate, silica or clay.
 4. Thecomposition of claim 3, wherein said metal oxide is zinc oxide,magnesium oxide, titanium oxide, yellow iron oxide, calcium oxide orlead oxide.